Mechanism of Singlet Fission in Carotenoids from a Polyene Model System.

Singlet fission (SF) is the process of formation of multiple excitons (triplet) from a locally excited singlet state. The mechanism of SF in polyacenes has been shown to proceed via a charge transfer intermediate state. However, carotenoids are not understood in the context of SF. This is possibly due to the complicated multireference nature of the low-lying excited states of carotenoids and the presence of a dark 21Ag state below the optically bright 1Bu state. In this work, we show that the dark Ag state in polyenes and/or carotenoids, along with the charge transfer states, plays a pivotal role in the SF process. We notice that the relative importance of these states varies with a change in geometry and the overall presence of multiple pathways is crucial to the success of the SF process in carotenoid aggregates and disordered geometries.

Excited-state proton transfer in a 2-aminopyridine dimer: a surface hopping study.

We present a theoretical investigation of the excited-state intermolecular proton transfer process in a 2-aminopyridine dimer. Previous experimental and theoretical studies on this doubly hydrogen bonded system have attributed an ultrafast 50 fs timescale to the process at low excitation wavelengths and have shown that it involves access to the charge transfer (CT) states of the dimer. We have carried out a trajectory-based surface hopping study of the proton transfer process. To this end, we have further studied the key intersections between locally excited (LE) and CT states that facilitate the proton transfer as well as the eventual ground state return at the XMS-CASPT2 level of theory. The dynamical simulations to investigate the charge transfer-driven event are performed at both the XMS-CASPT2 and TDDFT levels of theory. Trajectories are initiated from the excited states that are either already of CT character or become so upon a short extension of the NH bond. This kind of dynamics is found to be ultrafast with a timescale of about 100 fs, where the dimer rapidly accesses the LE/CT intersection regions en route to single proton transfer. After the transfer, some trajectories are also able to reach the ground state as well through a non-adiabatic transition. In contrast, trajectories that are initiated on an LE state remain on states of that character and do not show proton transfer. However, additionally providing 3 or 4 quanta of initial excitation to the NH stretch was found to promote CT state-driven proton transfer in the dimer.

N-H photodissociation dynamics of electronically excited aniline: a three dimensional time-dependent quantum wavepacket study.

We have simulated the dynamics of 1πσ* state-mediated nonadiabatic N-H bond dissociation in photo-excited aniline (C6H5NH2). A three electronic state diabatic model potential, involving the ground, 1ππ*, and 1πσ* diabatic states, and focussing on the NH2 degrees of freedom alone is constructed using XMS-CASPT2 energies. Using a kinetic energy operator in the polyspherical framework, wavepacket dynamics in three vibrational modes, viz. NH stretch, NH2 out-of-plane wag and torsion, is carried out using the Chebyshev propagation scheme. For optically bright 1ππ* excitation, the wavepacket can access the 1πσ*/1ππ* and 1ππ/1πσ* conical intersections that lie en route to dissociation. For both intersections, NH2 out-of-plane wag and torsional motions are the most dominant coupling coordinates. Carrying out dynamics with initial wavepackets varying in excitation in the three degrees of freedom, we probe their roles in the evolution of the state populations, probability densities, and product branching for the NH dissociation process.

Methodology to reduce 6D patient positional shifts into a 3D linear shift and its verification in frameless stereotactic radiotherapy.

The aim of this article is to derive and verify a mathematical formulation for the reduction of the six-dimensional (6D) positional inaccuracies of patients (lateral, longitudinal, vertical, pitch, roll and yaw) to three-dimensional (3D) linear shifts. The formulation was mathematically and experimentally tested and verified for 169 stereotactic radiotherapy patients. The mathematical verification involves the comparison of any (one) of the calculated rotational coordinates with the corresponding value from the 6D shifts obtained by cone beam computed tomography (CBCT). The experimental verification involves three sets of measurements using an ArcCHECK phantom, when (i) the phantom was not moved (neutral position: 0MES), (ii) the position of the phantom shifted by 6D shifts obtained from CBCT (6DMES) from neutral position and (iii) the phantom shifted from its neutral position by 3D shifts reduced from 6D shifts (3DMES). Dose volume histogram and statistical comparisons were made between [Formula: see text] and [Formula: see text]. The mathematical verification was performed by a comparison of the calculated and measured yaw (γ°) rotation values, which gave a straight line, Y = 1X with a goodness of fit as R 2 = 0.9982. The verification, based on measurements, gave a planning target volume receiving 100% of the dose (V100%) as 99.1 ± 1.9%, 96.3 ± 1.8%, 74.3 ± 1.9% and 72.6 ± 2.8% for the calculated treatment planning system values TPSCAL, 0MES, 3DMES and 6DMES, respectively. The statistical significance (p-values: paired sample t-test) of V100% were found to be 0.03 for the paired sample [Formula: see text] and 0.01 for [Formula: see text]. In this paper, a mathematical method to reduce 6D shifts to 3D shifts is presented. The mathematical method is verified by using well-matched values between the measured and calculated γ°. Measurements done on the ArcCHECK phantom also proved that the proposed methodology is correct. The post-correction of the table position condition introduces a minimal spatial dose delivery error in the frameless stereotactic system, using a 6D motion enabled robotic couch. This formulation enables the reduction of 6D positional inaccuracies to 3D linear shifts, and hence allows the treatment of patients with frameless stereotactic radiosurgery by using only a 3D linear motion enabled couch.